U.S. patent number 3,860,501 [Application Number 05/365,376] was granted by the patent office on 1975-01-14 for photosensitive copper (i) complexes and the use thereof in photographic development.
This patent grant is currently assigned to Eastman Kodak Company. Invention is credited to Henry J. Gysling.
United States Patent |
3,860,501 |
Gysling |
January 14, 1975 |
PHOTOSENSITIVE COPPER (I) COMPLEXES AND THE USE THEREOF IN
PHOTOGRAPHIC DEVELOPMENT
Abstract
A novel copper (I) complex having the formula Cu[P(OR).sub.3
].sub.4 BAr.sub.4 Wherein R is alkyl or aryl, and Ar is aryl is
employed as an actinic radiation sensitive element in an imaging
process comprising imagewise exposing a support carrying the copper
(I) complex to actinic light and developing an image by chemical or
physical development. The complex has excellent speed and may be
handled in room light prior to development.
Inventors: |
Gysling; Henry J. (Rochester,
NY) |
Assignee: |
Eastman Kodak Company
(Rochester, NY)
|
Family
ID: |
23438641 |
Appl.
No.: |
05/365,376 |
Filed: |
May 30, 1973 |
Current U.S.
Class: |
205/126;
427/97.3; 430/270.1; 205/187; 430/315; 430/417; 556/13; 987/217;
987/303; 427/77; 427/145; 430/413; 556/7 |
Current CPC
Class: |
C07F
9/141 (20130101); C07F 9/02 (20130101); G03C
1/735 (20130101) |
Current International
Class: |
C07F
9/00 (20060101); C07F 9/141 (20060101); C07F
9/02 (20060101); G03C 1/735 (20060101); G03C
1/73 (20060101); G03c 005/00 (); G03c 005/24 ();
G03c 001/00 () |
Field of
Search: |
;96/48R,48PD,88,38.4
;204/38B,15 ;260/438.1 ;117/13E,212 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Torchin; Norman G.
Assistant Examiner: Louie, Jr.; Won H.
Attorney, Agent or Firm: Rosenstein; A. H.
Claims
We claim:
1. A photographic composition comprising a hydrophilic polymeric
binder and a copper (I) complex having the formula
Cu[P(OR).sub.3 ].sub.4 BAr.sub.4
wherein R is alkyl containing from about one to six carbon atoms or
aryl containing from about 6 to about 12 carbon atoms and Ar is
aryl containing from about 6 to about 12 carbon atoms.
2. The composition of claim 1 wherein the weight ratio of complex
to binder is from 3:1 to 1:2.
3. A photographic element comprising a support and a photosensitive
copper (I) complex having the formula
Cu[P(OR).sub.3 ].sub.4 BAr.sub.4
wherein R is alkyl containing from one to six carbon atoms or aryl
containing from 6 to 12 carbon atoms and Ar is aryl containing from
6 to 12 carbon atoms in a hydrophilic polymeric binder.
4. The photographic element of claim 3 wherein the weight ratio of
complex to binder is 3:1 to 1:2.
5. A photographic element comprising a support having inbibed
therein a photosensitive copper (I) complex having the formula
Cu[P(OR).sub.3 ].sub.4 BAr.sub.4
wherein R is alkyl containing from one to six carbon atoms or aryl
containing from 6 to 12 carbon atoms and Ar is aryl containing from
6 to 12 carbon atoms.
6. In a process of developing an image in a light sensitive element
comprising a support and a light sensitive copper material imbibed
into said support or dispersed in a hydrophilic polymeric binder
and coated onto said support by contacting the copper material with
a chemical developer comprising a reducing agent or physical
developer comprising a metal salt and a reducing agent therefor the
improvement comprising employing as said light sensitive copper
material a light sensitive copper (I) complex represented by the
formula
Cu[P(OR).sub.3 ].sub.4 BAr.sub.4
wherein R is alkyl containing from one to six carbon atoms or aryl
containing from 6 to 12 carbon atoms and Ar is aryl containing from
6 to 12 carbon atoms.
7. The process of claim 6 wherein R is alkyl containing from one to
six carbon atoms and Ar is phenyl.
8. The process of claim 7 wherein the copper (I) complex has the
formula
Cu[P(OCH.sub.3).sub.3 ].sub.4 B(C.sub.6 H.sub.5).sub.4.
9. The process of claim 7 wherein the copper (I) complex has the
formula
Cu[P(OC.sub.2 H.sub.5).sub.3 ].sub.4 B(C.sub.6 H.sub.5).sub.4.
10. In a process of developing an image in a light sensitive
element comprising a support having coated thereon a light
sensitive copper material by contacting the copper material with a
chemical developer comprising a reducing agent or a physical
developer comprising a metal salt and a reducing agent therefor,
the improvement comprising imbibing into the support a solution of
a copper (I) complex having the formula
Cu[P(OR).sub.3 ].sub.4 BAr.sub.4
wherein R is alkyl containing from one to six carbon atoms or aryl
containing from 6 to 12 carbon atoms and Ar is aryl containing from
6 to 12 carbon atoms.
11. In a process of developing an image in a light sensitive
element comprising a support having coated thereon a light
sensitive copper material by contacting the copper material with a
chemical developer comprising a reducing agent or physical
developer comprising a metal salt and a reducing agent therefor the
improvement comprising coating the support with a copper (I)
complex having the formula
Cu[P(OR).sub.3 ].sub.4 BAr.sub.4
whrein R is alkyl containing from one to six carbon atoms or aryl
containing from 6 to 12 carbon atoms and Ar is aryl containing from
6 to 12 carbon atoms, in a hydrophilic binder, and subsequently
developing an image.
12. The process of claim 11 wherein the hydrophilic binder is
cellulose acetate.
13. The process of claim 6 wherein the latent image is developed in
a physical development bath comprising a metal salt and a reducing
agent therefor.
14. The process of claim 13 wherein the physical development bath
contains a copper salt and a reducing agent therefor.
15. The process of claim 13 wherein the physical development bath
contains a nickel salt and a reducing agent therefor.
16. The process of claim 6 wherein the latent image is developed in
a chemical development bath comprising a reducing agent.
17. The process of claim 16 wherein the chemical development bath
contains paraformaldehyde.
18. The process of claim 6 wherein subsequent to developing the
image, the unexposed portions of the coated support are imagewise
exposed to actinic light and the resulting second latent image is
chemically or physically developed to an additional image.
19. A method of forming a printed circuit comprising
A. (1) dispersing into a hydrophilic polymeric binder a copper (I)
complex having the formula Cu[P(OR).sub.3 ].sub.4 BAr.sub.4 wherein
R is alkyl from one to six carbon atoms or aryl containing from 6
to 12 carbon atoms and Ar is aryl containing from 6 to 12 carbon
atoms or (2) imbibing a support with a copper (I) complex having
the formula Cu[P(OR).sub.3 ].sub.4 BAr.sub.4 wherein R is alkyl
from one to six carbon atoms or aryl containing from 6 to 12 carbon
atoms and Ar is aryl containing from 6 to 12 carbon atoms,
B. imagewise exposing the coated support to actinic light and
C. physically developing metal on the exposed areas from a physical
development bath comprising a metal salt and a reducing agent
therefor and
D. electroplating additional metal over the physically developed
metal image to build up the metal layer.
Description
This invention relates to photography and more particularly to a
novel copper (I) complex and a process of forming images in a light
sensitive element comprising exposing a support carrying the
photosensitive copper (I) complex to actinic light and developing
the image.
U.S. Pat. NO. 3,658,534, issued Apr. 25, 1972, describes
photosensitive polymers comprising simple metal salts bonded to
oxygen, sulfur phosphorous, nitrogen, or halogen atoms by
coordination bonds.
It is known in the art to employ certain copper (I) salts with
silver halide emulsion layers to be exposed to actinic light and
developed to an image. U.S. Pat. No. 3,565,622, issued Feb. 23,
1971, describes the use of cuprous thiocyanate with silver halide
to form a visible image after development with an amine complexing
agent. Additionally some species of copper (I) complexes with
ligands and anions are described in S. J. Lippard and P. S.
Welcher, Inorganic Chemistry, Vol. 11, No. 1, 1972 (pages 6 to
11).
Thermographic copy sheets incorporating certain copper (I)
complexes as the heat sensitive component are described in U.S.
Pat. No. 3,505,093, issued Apr. 7, 1970. This patent describes the
imagewise exposure to heat of certain complexes to produce an
image.
German Pat. No. 950,428, issued Oct. 11, 1956, describes the use of
certain copper (I) salts such as cuprous chloride as photosensitive
compounds. These salts are, however, insensitive to light in the
dry state and must be moistened to provide light sensitivity.
Further, the copper (I) salts have poor speed and are unstable in
air.
The use of cuprous oxide as a photosensitive compound has been
disclosed in British Pat. No. 1,306,362. These compounds, however,
are not photosensitive to light unless moistened and are not
colorless and leave an undesirable background with poor image
differential.
No class of copper compounds has been found in the prior art that
(A) will form a well defined image after (1) imagewise exposure to
actinic light at comparative high speed and (2) development, (B)
that can be handled in normal room light, (C) that can be exposed
in a dry state, and (D) is stable to humidity and oxidation in the
atmosphere.
It is appreciated that the photosensitive copper materials of the
prior art are exceedingly slow speed in that they must be exposed
to light or radiation for a long time in order to obtain a
developable image. The novel copper (I) complexes of this invention
are high speed in comparison with other copper materials and in
most instances reach projection speed range which is less than
10.sup.3 ergs/cm.sup.2.
The preparation of printed circuits has generally comprised the
imagewise exposure of a photoresist material followed by removal of
exposed or unexposed areas and etching and subsequent
electroplating. This method is expensive, does not allow for
room-light handling, the raw stock is generally unstable, the
bleaching or etching steps pose solution disposal problems and
requires a multitude of process steps in a great deal of
equipment.
Accordingly, it is an object of this invention to provide a method
of exposing a photosensitive copper material and developing an
image that is resistant to oxidation and stable in the pressure of
moisture.
It is another object of this invention to provide novel copper (I)
complexes.
Still another object of this invention is to provide novel copper
(I) complexes which form images after high speed, imagewise
exposure to actinic light and physical development.
It is another object of this invention to provide a method of
imagewise exposing copper (I) complexes to actinic light to form
catalytic centers for development employing physical
developers.
Still another object of this invention is to provide copper (I)
complexes that have sensitivity restricted to the UV region
allowing their imagewise exposure to actinic radiation and
development under ambient lighting conditions.
Still an additional object of this invention is to provide printed
circuits by coating a support with a photosensitive copper (I)
complex and exposing imagewise to actinic light and developing the
exposed portions of the element by physical development of the
latent image.
These objects of the invention are accomplished by employing a
novel actinic radiation sensitive copper (I) complex represented by
the formula
Cu[P(OR).sub.3 ].sub.4 BAr.sub.4
wherein R is alkyl or aryl and Ar is aryl as the light sensitive
material in a process comprising imagewise exposing a support
carrying a light sensitive material to actinic light and providing
an image by either physical or chemical development.
The novel copper (I) complex is represented by the formula
Cu[P(OR).sub.3 ].sub.4 BAr.sub.4
wherein R is either alkyl preferably containing from one to six
carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl,
pentyl, hexyl and the like or aryl such as phenyl, tolyl, naphthyl,
anthracenyl, ethyl phenyl, and the like preferably containing from
6 to 12 carbon atoms. Ar is aryl such as phenyl, naphthyl, tolyl,
butyl phenyl, and the like preferably containing from 6 to 12
carbon atoms. Some examples of BAr.sub.4 are
tetraphenylborate
tetra-o-tolylborate
tetra-m-tolylborate
tetra-p-tolyborate
tetra-p-ethylphenylborate
tetra-p-propylphenylborate
tetra-3,4,5-trimethylphenylborate
tetra-m-methoxyphenylborate
tetra-p-methoxyphenylborate
tetra-p-ethoxyphenylborate
tetra-p-bromophenylborate
tetra-m-chlorophenylborate
tetra-p-chlorophenylborate
tetra-2,3,4,5-tetrachlorophenylborate
tetra-m-fluorophenylborate
tetra-p-fluorophenylborate
tetra-m-trifluoromethylphenylborate
tetra-p-trifluoromethylphenylborate
tetra-perfluorophenylborate
tetra-p-dimethylaminophenylborate
tetra-p-acetamidephenylborate
tetra-4-biphenylborate
tetra-4-phenoxyphenylborate
tetra-1-naphthylborate
tetra-2-naphthylborate
tetra-9-anthranylborate
tetra-9-phenanthrylborate
tetra-2- phenylethynylborate
tetra-1-pyrrolylborate
tetrapyrazol-1-yl-borate
tetra-1-indolyborate
tetra-2-furylborate
tetra-5-methyl-2-furylborate
tetra-2-thienylborate
tetra-2-selenylborate and the like.
The terms "alkyl" and "aryl" as used herein include substituted
alkyl and substituted aryl such as chloroethyl, bromophenyl, methyl
phenyl, phenyl butyl, and the like. It is only necessary that the
substituent not interfere with the photosensitivity of the
complex.
Complexes useful herein are
Cu[P(OCH.sub.3).sub.3 ].sub.4 B(C.sub.6 H.sub.5).sub.4
Cu[P(OC.sub.6 H.sub.5).sub.3 ].sub.4 B(C.sub.6 H.sub.5).sub.4
Cu[P(OC.sub.2 H.sub.5).sub.3 ].sub.4 B(C.sub.6 H.sub.5).sub.4
Cu[P(OCH.sub.3).sub.3 ].sub.4 B(CH.sub.3 C.sub.6 H.sub.4).sub.4
Cu[P(OCH.sub.3 C.sub.6 H.sub.4).sub.3 ].sub.4 B(C.sub.6
H.sub.5).sub.4
Cu[P(OC.sub.4 H.sub.9).sub.3 ].sub.4 B(C.sub.6 H.sub.5).sub.4
and the like.
Preferred complexes are
Cu[P(OCH.sub.3).sub.3 ].sub.4 B(C.sub.6 H.sub.5).sub.4
and
Cu[P(OC.sub.2 H.sub.5).sub.3 ].sub.4 B(C.sub.6 H.sub.5).sub.4
The novel complexes may be prepared by reacting cuprous salts such
as cuprous chloride with a phosphite having the formula
P(OR).sub.3
wherein R is as described above. The cuprous salt and the phosphite
are generally mixed in an inert solvent such as chloroform,
methylene chloride, ethylene chloride, and the like. The reactants
may be mixed at room temperature without the aid of catalysts. To
the reactants is added a salt of tetraarylboron such as sodium
tetraphenylboron, generally in solution with a solvent such as
ethanol or methanol or the like. The cuprous salt and phosphite are
mixed at approximately 1:4 to 1:5 molar proportions. As the
reaction is exothermic, the copper (I) complex is crystallized out
by cooling, generally to about -15.degree.C. to about
5.degree.C.
Alternatively, the copper (I) complex may be prepared by reducing a
copper (II) salt. This method entails reducing a cupric salt such
as cupric chloride in a solvent such as ethanol or methanol,
propanol or butanol with excess trialkyl phosphite or triaryl
phosphite. The molar proportion of phosphite to cupric salt is
generally from about 4.5:1 to about 6:1. The reactants including
the alcohol may be mixed at room temperature if desired and without
the aid of a catalyst. The resulting product is further reacted
with a salt of tetraarylboron such as NaB(C.sub.6 H.sub.5).sub.4.
The molar proportion of tetraarylboron salt to the above reaction
product may generally be equalmolar The copper (I) complex is then
crystallized out by cooling, generally to about -15.degree.C. to
about 5.degree.C.
If the copper (II) salt is reacted with triaryl phosphite
[P(OAr).sub.3 ] in the presence of a lower alkanol, a solvolysis
occurs such as in the following reaction.
4.5P(OAr).sub.3 + Cu(II) .sup.ROH .fwdarw. Cu[P(OR).sub.3 ].sub.4
.sup.+ This can be further reacted with NaB(C.sub.6 H.sub.5).sub.4
as illustrated above.
The photosensitive complex may be either imbibed into a support or
coated onto a support in a polymeric binder, typically a
hydrophilic binder prior to imagewise exposure. Thus, the substrate
may be dipped in a bath of the complex and dried to render the
element photosensitive or, if desired, the complex may be added to
a binder solution and coated onto the support by any means, such as
dip coating, brushing, rolling, spraying or the like and then
dried. This method is specifically useful in forming printed
circuits.
The binder used as a vehicle for the photosensitive complex may be
any of the hydrophilic binders used in photographic elements,
including natural materials such as gelatin albumin, agar-agar, gum
arabic and alginic acid, and synthetic materials such as polyvinyl
alcohol, polyvinyl pyrrolidone, cellulose ethers, partially
hydrolyzed cellulose acetate and the like. The complex may be used
with varying amounts of binder material. Preferably the complex to
binder weight ratio is from about 3:1 to about 1:2.
The complex may be either imbibed into or coated onto any substrate
typically used for photographic elements. Support materials used
herein are subject to wide variation. Glass may be employed as may
be metals such as aluminum, copper, zinc, and tin. Conventional
film bases, such as cellulose acetate, cellulose nitrate, cellulose
acetate butyrate, poly(ethylene terephthalate), polystyrene and
paper are also used. The preferred support materials, when the
process is to be used to form an element for use as a printed
circuit are poly(ethylene terephthalate), polyimides, and cellulose
acetate. The supports generally suitable for imbibing are porous
supports such as paper. Generally the supports should contain from
about 1 to about 200 mgs. per square foot of copper (I).
The coated support is dried and may then be stored for convenient
periods of time prior to imagewise exposure as the complexes are
not sensitive to ambient light, nor to the humidity in the
atmosphere.
The elements are typically exposed through a pattern of actinic
light providing a latent image corresponding to the exposed or
unexposed areas. The complexes of this invention are sensitive to
actinic light such as ultraviolet rays generally in the wavelength
range of 1,800 to 4,000 Angstroms. Many sources of ultraviolet
light may be used such as high vapor mercury lamps, carbon are
lamps, and the like. It is noted that the novel complexes may be
exposed at projection speed range which has been heretofore
unattainable with copper materials.
The latent image in the exposed element can be developed into a
desired metal image, typically a visible image, by either physical
development or chemical development.
The physical development may take place in any conventional
physical developing bath. The physical development bath generally
contains metal ions in salt form and a reducing agent for the metal
ions. Typical physical developer solutions are well known (see
Hornsby, Basic Photographic Chemistry, (1956) 66, and Mees and
James, ed. The Theory of the Photographic Process, 3rd edition
(1966), 329-331, and U.S. Pat. No. 3,650,748 to Yudelson et al.,
issued Mar. 21, 1972) and contain the metallic ions such as silver,
copper, iron, nickel, or cobalt necessary to form a visible image
at and in the vicinity of the nucleating centers.
The preferred metal salts are water soluble salts such as silver
nitrate, cupric salts such as copper chloride, copper nitrate,
copper sulfate, copper formate, copper acetate and the like, and
nickel salts such as nickel chloride, nickel bromide, nickel
sulfate, nickel nitrate, nickel formate and the like.
Typical reducing agents used in the physical developer include, for
example, polyhydroxy-substituted aryl compounds such as
hydroquinones, catechols and pyrogallols; ascorbic acid
derivatives; amino-phenols; p-phenylenediamines, and the like
developing agents used in the photographic art. Particular examples
of reducing agents for physical developer solutions are
2-methyl-3-chlorohydroquinone, bromohydroquinone, catechol,
5-phenyl-catechol, pyrogallol monomethyl ether
(1-methoxy-2,3-dihydroxybenzene) and 5-methylpyrogallol monomethyl
ether, isoascorbic acid, N-methyl-p-aminophenol,
dimethyl-p-phenylene diamine, 4-amino-N,N-di(n-propyl) aniline and
6-amino-1-ethyl 1,2,3,4-tetrahydroquinoline and borane reducing
agents such as amine boranes, borohydrides and the like.
The preferred physical development baths include the Copper Enthone
developer baths (A trademark of Enthonics Corp.) containing copper
sulfate, formaldehyde, Rochelle salt and nickel sulfate.
The physical developer solutions can, in addition to the metal
salt, reducing agent, and a complexing agent such as Rochelle salt
or other ligands for the metal salt, include a variety of other
materials to facilitate maintenance and operation of the developer
and to improve the quality of the developed image, such as acids
and bases to adjust pH, buffers, preservatives, thickening agents,
brightening agents, and the like. The rate of development can be
increased, and hence the time of development decreased, by adding
to the developer solution a surfactant such as an alkyl metal salt
of a sulfated fatty acid, e.g., dodecyl sodium sulfate.
The proportions in which the various components of the physical
developer are present in the developer solution can vary over a
wide range. Suitable concentrations of reducible heavy metal salt
can range from about 0.01 mole to about 1.0 mole of metal salt per
liter of solution. The upper limit of concentration is dependent
upon the solubility of the particular metal salt employed.
Preferably, the solution is about 0.1 molar to about 0.3 molar with
respect to the heavy metal salt. The relative proportions of metal
salt and complexing agent are dependent upon the particular heavy
metal salt or salts and the particular complexing agent or agents
which are employed. As a general rule, sufficient complexing agent
should be incorporated to "tie up" the reducible heavy metal ions
which are in solution and to lessen the tendency of these metal
ions to be reduced prior to use of the developer solution.
Depending upon the particular heavy metal salt and the particular
complexing agent which is employed, the amount of complexing agent
present typically can vary from about 0.2 to about 10 moles of
complexing agent per mole of metal salt present. Typically, the
reducing agent can be present in amounts from about 0.01 mole to
about 5 moles of reducing agent per mole of metal salt present in
the solution. In order to permit the developer solution to be
utilized for its maximum life, at least one equivalent of reducing
agent should be present in the solution for each equivalent of
reducible heavy metal salt.
The physical developers are operative over a wide range of pH.
However, since the borane reducing agents undergo an acid catalyzed
hydrolytic reaction which reduces their stability during storage,
it is preferred that the physical developers be maintained at a
moderately alkaline pH of about 8 to 11, and preferably of about
8.5 to 9.5. Nevertheless, the physical developers can be used under
acidic conditions, as low as pH 3, if such conditions are
advantageous for the particular photographic process in which they
are used. The physical developer solution can be brought to the
desired pH by addition of an appropriate amount of a suitable base;
for example, ammonium hydroxide or sodium hydroxide, and can be
maintained at the desired pH by addition of a suitable buffering
system, for example, sodium carbonate and sodium bicarbonate. Other
materials which can be used to adjust the pH to the desired range
and buffers which will maintain the pH in that range can be readily
determined by those skilled in the art.
The exposed elements may be developed chemically by immersing in
solutions comprising amino phenols, phenylenediamines,
hydroquinones, amino-dialkylanilines, heterocyclic chemical
developers such as phenyl pyrazolidone and the like. A complete
description of chemical developers which may be used herein can be
found in Mees and James, The Theory of the Photographic Process,
3rd Edition, Chapter 13 (1966).
The process outlined above may yield a positive or negative image
depending on the complex used and the physical development process.
Thus, a negative image may be obtained by physically developing any
of the copper (I) complexes of this invention with a copper
physical developer and the complex having the formula
Cu[P(OC.sub.2 H.sub.5).sub.3 ].sub.4 B(C.sub.6 H.sub.5).sub.4
may be developed with a nickel developer to a positive image. It is
noted that a negative image may be attained using this complex by
developing with a copper physical developer.
The developed elements of the invention are especially advantageous
as they have add-on capabilities. That is, the complexes remaining
in the undeveloped areas are not affected by room light and
portions of the developed element may be further imagewise exposed
to actinic light and developed to produce an additional image on
the element.
The process of this invention is particularly useful in forming
elements for use as printed circuits. In this method, insulating
supports are either imbibed with the copper (I) complexes or coated
with the complexes in a binder and dried. The coated supports are
imagewise exposed to actinic light so that the exposed portions are
catalytic to the deposition of a metal such as copper, silver or
nickel by physical development. The exposed element is then
physically developed in a metal salt containing bath such as in a
copper physical development bath and the metal such as copper is
deposited and built up on the exposed portions of the element only.
The element may then be dried, and if desired, a heavier build up
of metal may be achieved in the exposed areas by electroplating
over the element. The completed element may then be used to form a
printed circuit. This method is simple and inexpensive and requires
no addenda or special equipment.
The following examples are included for a further understanding of
the invention.
Example 1
A copper (I) complex was formed by adding 2.6 g of cuprous chloride
to a solution of 30 ml of triethyl phosphite in 200 ml of
chloroform. A clear, colorless solution resulted after brief
stirring. To the solution was added a solution of 10.3 g of sodium
tetraphenylboron in 80 ml of ethanol. After stirring for 1 hour,
the solution was diluted to 2 liters with ethanol and 600 ml of
methanol was added. The solution was cooled for 5 days in a freezer
and a heavy crop of white crystals had deposited. The crystals were
filtered on a coarse sintered glass filter, washed with ethanol,
and vacuum-dried. A yield of 16.2 g of a complex having the
formula
Cu[P(OC.sub.2 H.sub.5).sub.3 ].sub.4 B(C.sub.6 H.sub.5).sub.4
was obtained. The complex was soluble in benzene, chloroform,
methanol and ethyl ether but only slightly soluble in ethanol. The
solid state reflectance spectrum of the complex showed an
absorption maximum at 280 nm.
Example 2
A copper (I) complex was prepared by adding 4.8 g of
Cu(NO.sub.3).sub.2 .3H.sub.2 O to a solution of 10 ml of
2,2-dimethoxypropane in 30 ml methanol. After stirring for 5
minutes the solution was cooled in an ice bath and 35 ml of
trimethyl phosphite was slowly added. To the solution was then
added 6.8 g of NaB(C.sub.6 H.sub.5).sub.4 in 40 ml of methanol. The
resulting white precipitate was filtered, washed with methanol and
ether, and vacuum-dried for 20 hours over P.sub.2 O.sub.5.
The yield was 8.3 g of a complex having the formula
Cu[P(OCH.sub.3).sub.3 ].sub.4 B(C.sub.6 H.sub.5).sub.4
which was soluble in acetone and chloroform but insoluble in ether.
The solid state reflectance spectrum of the complex showed an
absorption maximum at 278 nm.
Example 3
The procedure of Example 2 was repeated substituting
triphenylphosphite for the trimethylphosphite. Due to the
solvolysis reaction, the same product was achieved.
Example 4
The procedure of Example 2 was repeated substituting tri-p-tolyl
phosphite for the trimethylphosphite and the resulting product had
the formula
Cu[P(OCH.sub.3).sub.3 ].sub.4 B(C.sub.6 H.sub.5).sub.4
Example 5
A copper (I) complex was prepared by adding 35 ml of P(OC.sub.6
H.sub.5).sub.3 to 3.4 g of Cu Cl.sub.2 .2H.sub.2 O in 75 ml
n-butanol. To the clear solution was added 250 ml of methanol and a
solution of 6.8 g of NaB(C.sub.6 H.sub.5).sub.4 in 75 ml of
methanol. The solution was cooled in a freezer overnight and the
resulting white crystals were filtered out and vacuum-dried. A
yield of 11 g of a complex having the formula
Cu[P(OC.sub.4 H.sub.9).sub.3 ].sub.4 B(C.sub.6 H.sub.5).sub.4
was obtained. The complex was soluble in chloroform, acetone and
ether but insoluble in ethanol.
Example 6
A solution was prepared by dissolving one g of the copper (I)
complex prepared in Example 1 in 40 ml of a 10 percent by weight
solution of cellulose acetate in acetone-methoxyethanol (50 : 50
V/V). The solution of complex and binder was coated on gel-subbed
poly(ethylene terephthalate) at a 3 mil wet thickness.
The coated support was imagewise exposed to actinic light under a
360-watt Gates lamp for 30 seconds and a distance of 12 inches. The
image was developed by immersing the coated support in a solution
of 50 mg hydrazine-bisborane in 50 ml of a nickel solution
comprising
68.75 g of NiCl.sub.2 .6H.sub.2 O
45 g ethylenediamine
225 g K CH.sub.3 CO.sub.2
3 liters H.sub.2 O
The resulting element had a nickel deposit only in the unexposed
areas of the film.
A positive image was achieved by immersing another sample of the
exposed coated support in a physical developer comprising 65 mg of
methyl hydrazinebisborane dissolved in 100 ml of the above nickel
solution.
Example 7
The coated support of Example 6 was imagewise exposed to actinic
light for 10 seconds under a Gates lamp at a distance of 12 inches.
The image was developed by immersing in a Copper Enthone developer
containing copper sulfate, formaldehyde, Rochelle salt, and nickel
sulfate at 70.degree.C. A heavy black copper deposite was formed in
the exposed areas only.
The threshold exposure at 254 nm of samples of the film of Examples
6 and 7 was determined by irradiating at 254 nm with a UVS-11
Mineralight lamp through a series of neutral density filters. The
minimum exposure necessary for development in the nickel developer
of Example 6 was found to be 1.08 .times. 10.sup.5 ergs/cm.sup.2
and the minimum exposure necessary for development in the developer
of Example 7 was found to be 3800 ergs/cm.sup.2. This is compared
to a similar copper (I) complex having the formula Cu[P(C.sub.6
H.sub.5).sub.3 ].sub.3 BH.sub.3 CN.CHCl.sub. 3 which when subjected
to the same exposure and development required a minimum exposure of
1.1 .times. 10.sup.6 ergs/cm.sup.2.
Example 8
A paper support was imbibed with a solution of 1 g of the copper
(I) complex of Example 2 dissolved in 20 ml of acetone. The coated
support was imagewise exposed to actinic light under a UVS-11
Mineralight lamp for 10 seconds at a distance of 1.5 centimeters. A
yellow coloration was produced in the exposed area. The exposed
element was placed under fluorescent lighting for 2 days and no
change in the image was observed. The exposed element was developed
by immersing in a Copper Enthone developer at 65.degree.C. for 60
seconds. A dark copper image was developed in the exposed areas
only. The minimum exposure necessary for development here was found
to be only 870 ergs/cm.sup.2.
Another sample of the coated strip was imagewise exposed to actinic
light under a Model 437 Nano Pulser (Xenon Corporation) in
different areas with from 1 to 4 pulses. Subsequent immersions in
the Copper Enthone developer for 30 seconds resulted in an image
formed in all 4 irradiated areas.
Example 9
A film was prepared by dissolving 0.5 g of the copper (I) complex
of Example 2 in 10 ml of a 10 percent by weight 50 : 50 V/V
acetone-methoxyethanol solution of cellulose acetate and coating
the solution on a unsubbed cellulose acetate film base at a wet
thickness of 6 mils.
The coated film was imagewise exposed to actinic light under a UVS
-11 Mineralight lamp for 5 seconds at a distance of 1.5 cm. After a
2-minute immersion in Copper Ethone Developer at 70.degree.C., a
copper image was developed in the exposed areas only.
Example 10
A paper support was imbibed with a solution of 0.5 g of the copper
(I) complex of Example 5 in 10 ml of acetone and imagewise exposed
to actinic light under a UVS-11 Mineralight lamp for 10 seconds at
a distance of 1.5 cm.
The exposed element was immersed in a Copper Enthone developer for
4 minutes at 70.degree.C. and a copper image was developed in the
exposed areas only.
Example 11
The substantial enhancement of photosensitivity of the novel copper
complexes of this invention was demonstrated by comparing the
development of these complexes to that of similar copper (I)
phosphite complexes in the following manner:
Paper supports were imbibed in solutions of Cu[P(OCH.sub.3).sub.3
].sub.4 NO.sub.3 and Cu[P(OCH.sub.3).sub.3 ].sub.4 C1 and imagewise
exposed to actinic light under the UVS-11 Mineralight lamp at a
distance of 1.5 cm. for 5 minutes and immersed in the Copper Ethone
developer for several minutes and only a trace of physical
development appeared before fog appeared in the unexposed
areas.
This was compared to the 10 second exposure and 90 second
development obtained using the complex of Example 1 to form a
completely developed image and the 5 second exposure and 60 second
complete development obtained using the complex of Example 2.
The threshold exposures for development in Copper Enthone
developers at 60.degree.C for the complexes of Examples 1 and 2 at
275 nm are 430 ergs/cm.sup.2 and 150 ergs/cm.sup.2 respectively
while the threshold exposures for the complexes
Cu[P(OCH.sub.3).sub.3 ].sub.4 NO.sub.3 and Cu[P(OCH.sub.3).sub.3
].sub.4 C1 are substantially higher than 1 million
ergs/cm.sup.2.
Example 12
A solution comprising 10 ml of a 20 percent by weight solution of
poly(ethylacrylate-acrylic acid) in chloroform, 10 ml of a copper
(I) complex having the formula Cu[(OCH.sub.3).sub.3 P].sub.4
[B(C.sub.6 H.sub.5).sub.4 ] in chloroform (10 percent weight by
volume solution), and 4 drops of 1,4-butanediol diglycidylether was
coated onto a poly(ethyleneterephthalate) support at a wet
thickness of 5 mils. The coating was cured by heating at
40.degree.C overnight.
A printed circuit was prepared by imagewise exposing the dried
element to a low pressure mercury arc through a stainless steel
mask for 30 to 60 seconds. The exposed element was then physically
developed in a 1 : 1 Copper Enthone 400A-400B physical development
bath for 10 to 20 minutes at 32.degree.C.
The latent image was stable for 3-5 days and the process was
carried out under fluorescent light and normal room illumination
with no resultant fog. The printed circuit also was capable of
being added onto by re-exposing and developing with no fog
appearing in either the first or second image areas.
Example 13
A printed circuit was prepared by imbibing a support with a
solution comprising 2.5% Cu[P(OCH.sub.3).sub.3 ].sub.4 B(C.sub.6
H.sub.5).sub.4 in chloroform for 10 seconds. The coated support was
imagewise exposed to a low pressure mercury arc at 254 nm through a
stainless steel mask for 30 to 60 seconds and developed in Copper
Ethone developer at 32.degree.C. for 15 minutes.
Example 14
A solution of 0.5 g Cu[P(OCH.sub.3).sub.3 ].sub.4 B(C.sub.6
H.sub.5).sub.4 in 20 ml of 10 percent by weight cellulose acetate
solution in 1:1 acetone methoxyethanol was coated on an unsubbed
poly(ethylene terephthalate) to a wet thickness of 6 mils. The
coated film was imagewise exposed for 5 seconds under a 360-watt
Gates lamp at a distance of 12 inches and developed in the exposed
areas by immersing in a Copper Enthone developer solution at
40.degree.C.
The add-on property of this novel complex was demonstrated by
allowing the developed element to stand for 24 hours under ambient
conditions and then subjecting the developed film to an additional
5 seconds of a Gates lamp imagewise exposure. After immersion in
the Copper Enthone developer, development in the areas exposed to
the UV source during the second exposure as well as a build up of
the copper deposit in the areas developed after the first exposure
was achieved.
Example 15
A solution of 5 g of Cu[P(OCH.sub.3).sub.3 ].sub.4 B(C.sub.6
H.sub.5).sub.4 in 50 ml acetone was imbibed into a paper support
and dried. The coated paper was exposed imagewise for 5 seconds
under a UVS-11 Mineralight lamp at a distance of 1.5 cm. and
chemically developed by immersing for 10 seconds in a solution
containing 130 g of paraformaldehyde plus 120 g KOH and 1 liter of
water. Amplification of the invisible latent image to a visible
black image was achieved. The threshold exposure value at 254 nm
for this chemical development was 3 .times. 10.sup.3
ergs/cm.sup.2.
Although the invention has been described in considerable detail
with reference to certain preferred embodiments thereof, it will be
understood that variations and modifications can be effected
without departing from the spirit and scope of the invention as
described hereinabove.
* * * * *